CN1215329C - Calixarene bonded silica gel immobile phase preparing process - Google Patents
Calixarene bonded silica gel immobile phase preparing process Download PDFInfo
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- CN1215329C CN1215329C CN 03119093 CN03119093A CN1215329C CN 1215329 C CN1215329 C CN 1215329C CN 03119093 CN03119093 CN 03119093 CN 03119093 A CN03119093 A CN 03119093A CN 1215329 C CN1215329 C CN 1215329C
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Abstract
The present invention relates to a method for quickly preparing a chromatograph bonded stationary phase by the secondary reaction technology of a functional coupling agent. The preparing method comprises the following two steps: step one, preparing a precursor of gamma-epoxy propoxypropyl silica gel; step two, preparing calixarene phenol sodium salts from sodium hydride and calixarene as reactants and anhydrous toluene as a solvent under the condition of 70 to 80 DEG C, bringing the calixarene sodium salts to the surface of the precursor of the silica gel of the last step by a phase transfer catalyst of quaternary ammonium salts to react under the condition of 110 to 120 DEG C in nitrogen gas or argon gas to prepare a calixarene bonded silica gel stationary phase with a certain bonding concentration. The present invention has the advantages of simple and convenient method, low preparing cost and wide application scope of the preparing method. The prepared calixarene silica gel bonded stationary phase has the advantages of high surface bonding rate and high stability to acid, is suitable for the separation analysis of high performance liquid chromatographs, microcolumn liquid phase chromatographs and electric chromatographs, and is capable of being used as relevant separating materials.
Description
Technical field
The present invention relates to a kind of preparation method of calixarenes bonded silica gel stationary phase.
Background technology
Chromatography is a separate analytical technique with fastest developing speed, most widely used in the analytical chemistry in modern age, and developing into efficient, energy-conservation separation engineering technology, play an increasingly important role in various fields such as chemistry, biology and biotechnology, medicine and pharmacology, life sciences.The basic demand of stratographic analysis is the separation that realizes each component of potpourri, and the essence of separation then is based on the interactional difference between analyzed solute and moving phase and the stationary phase.Wherein, the development of high selectivity stationary phase is the core realm of chromatographic system.Numerous chromatographic stationary mutually in, silica gel and modified silica-gel development time are studied the most deeply the earliest, still occupy leading position at present.Its major advantage is: physical strength is good, and physical property such as specific surface area, pore structure, aperture and pore volume are easy to control, and the surface silicon alcohol radical has high reaction activity, can obtain multiple function stationary phase by chemical modification.Commercial at present silica gel and modified silica-gel kind are very abundant.The application that with octadecyl bonding silica particles (ODS) is the anti-phase type stationary phase of representative once accounted for more than 80% in the conventional compartment analysis of HPLC, became " broad spectrum type " chromatographic stationary phase.Yet along with the develop rapidly of medical science, life science and environmental science, the variation of separate object and complicated development to the chromatogram stationary phase have proposed challenge." exclusive type " emerging in large numbers of stationary phase of high selectivity emerged in an endless stream, mainly contained: for satisfy chiral stationary phase that drug enantiomer separates needs, adapt to biochemical protein bonded stationary phase of separating, the molecular imprinting stationary phase of crown ether, cyclodextrin, calixarenes stationary phase and obligatory type based on the supermolecule effect.In recent years, the needs that separate fast make the research and development of integral body of new generation or continuous bed chromatographic stationary phase obtain fast development.The exploitation of chromatographic stationary phase has also promoted the development of relevant isolation technics simultaneously.
{ CEC} is a kind of novel differential compartment analysis technology that development in recent years is got up to capillary electric chromatogram, is proposed first in 1974 by Pretorius; Be achieved by Jorgenson etc. in 1981.Since the nineties, CEC technology and theory obtain paying attention to and development, and relevant research report is geometric series to be increased.CEC inserts stationary-phase particle size, tube wall bonded stationary phase or makes the continuous bed form in capillary column, in conjunction with the pressure-driven phase that flows, solute is based on being separated in the difference of the different of partition factor between moving phase and stationary phase and self electrophoretic mobility with electroosmotic flow (EOF) or electroosmotic flow.As the hybrid of high performance liquid chromatography (HPLC) and Capillary Electrophoresis (CE), CEC has some and is better than both characteristics.
Compare with HPLC, the flat slug flow type of the EOF of CEC can overcome the discrete and plate height increase of chromatographic peak that HPLC para-curve flow pattern causes.The CEC post is imitated generally can reach 100,000-300, and 000plates/m, thereby can use shorter pillar, shorten the compartment analysis time.EOF results from filling surface, and its size is irrelevant with packing material size in theory.Can not produce pressure gradient as driving force, can adopt small particle size filler, reduce resistance to mass tranfer, improve the post effect.Although it is numerous different that HPLC and CEC exist from principle and range of application, stationary phase can be used for reference mutually, and the preparation of novel stationary phase is the important step of HPLC and CEC.
In recent years, based on the bonded stationary phase of Subjective and Objective effect, because the compatibility of its high selectivity and biological sample makes it to become the novel stationary phase that a class has potentiality.It mainly comprises: protein bonded stationary phase, crown ether bonded stationary phase, cyclodextrin bonded stationary phase, molecular imprinting stationary phase and calixarenes bonded stationary phase.
Protein is the big molecule of natural chirality, has the height stereoselectivity with the interaction of part, enzyme.Protein bonded stationary phase has unique advantage: multiple enantiomorph solute does not need derivatization just can directly split; Fractionation to physiological activator is also comparatively desirable.But protein bonded stationary phase remains deficiencies such as little at bonded amount, that cost is high, serviceable life is short at present.Crown ether bonded stationary phase crown ether is the big acyclic polyether compound with certain ring cavity of a class synthetic.Separate mainly optionally forming host-guest inclusion complex with kation or polar compound based on crown ether, the stability of Different Complex there are differences, thereby presents the chromatogram selective retention.In recent years, the research of relevant crown ether stationary phase mainly concentrates on Chiral Separation.Because crown ether, contain particularly that specific function base crown ether synthetic technology acquires a certain degree of difficulty, the cost height, thereby this class stationary phase progress is slow.Cyclodextrin bonded stationary phase cyclodextrin stationary phase is the novel stationary phase that closely grows up during the last ten years, also is the maximum important chiral stationary phase of a class of research.Twentieth century is since the nineties, and derivatized cyclodextrin bonded stationary phase has obtained developing rapidly.Cyclodextrin is carried out chemical modification, and introducing can form interactional groups such as π-π, hydrogen bond and dipole-dipole, has the Chiral Separation ability.But the ring cavity body is single, and related object object mainly is limited to neutral molecule.Molecularly imprinted polymer stationary phase (MIPs) is the inspiration that is subjected to the antibody of enzyme to have the characteristics of shape selective, grow up based on the host-guest effect, and be mainly used in the stationary phase of chiral resolution.MIPs has " memory " function to the spatial structure of microsphere, and the predetermined high selectivity based on the host-guest effect is arranged, and this is that traditional C P is not available.It is big that this class stationary phase prepares difficulty, and separate object is single, " memory " function poor reproducibility, thereby use limited.
Calixarenes is the macrocyclic compound that a class is formed by connecting by methylene by phenol units.This compounds has the outer rim of typical cave cavity configuration and functionalization, experiment confirm, and calixarenes can form stable containing complex compound with many ions and neutral molecule, thereby, by " third generation host molecule " after crown ether and cyclodextrin.Calixarenes can be discerned object by multiple non-covalent supermolecule effect, thereby realizes specific functions such as coordination, catalysis, mass transfer and energy conversion, makes it one of important research object that becomes supramolecular chemistry.Over nearly 20 years, the calixarenes chemistry is developed rapidly, and calixarenes is at the application potential in fields such as liquid film mass transfer, complexometric extraction, molecular probe, molecular device, sensor, liquid crystal, nonlinear optics, catalysis, analogue enztme and compartment analysis.
Utilize the molecular recognition effect of calixarenes, be expected to improve the selectivity of chromatographic resolution solute.In recent years, the calixarenes research that is used for liquid chromatography and Capillary Electrophoresis becomes one of focus.1993, Park etc. are used for high performance liquid chromatography to calixarenes first, sulfonation cup [6] is added in the moving phase, successfully separated metoxyphenol, amino-phenol and nitrophenol position isomer, separation is based on solute and calixarenes forms the stability difference of leading an object inclusion compound.1994, beginnings such as Shohat adopted calixarenes to make the position isomer that adjuvant separates chlorophenol, benzenediol, methylaniline in high performance capillary electrophoresis.Cheng Jieke etc. are adjuvant with sulfonation cup [4] aromatic hydrocarbons, have separated nitrophenol, amino-phenol and benzenediol isomeride, and post is imitated up to 3 * 10
5Plate/rice has been showed the application potential of calixarenes in separation science.Yet, the calixarenes poor solubility, when making adjuvant, strong uv absorption Interference Detection makes it to use limited in addition, and the research of calixarenes bonded stationary phase should be the main flow of development.
1993, Glennon etc. have prepared esterification cup [4 first, 6] aromatic hydrocarbons bonded stationary phase, be used to separate alkali metal ion, benzamide and amino-acid ester compounds, the bonding of finding cup [4] aromatic hydrocarbons has improved the separation selectivity to Na+ greatly, and experiment shows, the N-H in benzamide and the amino-acid ester can with the calixarenes ester carbonyl group by hydrogen bond and inducing action, form outer formula (beside-cavity) complex compound, thereby realize good separation.Gebauer etc. use tert-butyl group cup [4,6,8] fixed and have been separated to the methylpyrimidine isomeride, and effect obviously is better than ODS post and cyclodextrin post.After this, although relevant report calixarenes bonding phase kind is arranged successively seldom, and the bonding reaction applicable surface of being reported is narrow, the preparation process complexity.
Summary of the invention
Problem to be solved by this invention provides a kind of preparation method of calixarenes bonded silica gel stationary phase, and this method is easy, cost is lower, and the calixarenes bonded stationary phase of being synthesized has that bonded amount is higher, bonded layer is stable.
Technical scheme provided by the invention is: the preparation method of the silica gel bonded stationary phase of a kind of calixarenes, under blanket of nitrogen, in activated silica gel: coupling agent: the ratio of dry toluene 10g: 50mmoL: 100mL adds coupling agent γ-glycidoxy trimethoxy silane in the dry toluene, stir, add activated silica gel then, add triethylamine, oil bath is warming up to 110～120 ℃, stir, reaction is 6 hours under reflux state, stops heating, continues logical nitrogen until room temperature; Filter, solid toluene and washing with acetone, vacuum drying makes precursor silica gel; With sodium hydride and calixarenes is reactant, is solvent with the dry toluene, makes the calixarenes sodium phenolate under 70～80 ℃ of conditions; In the presence of the phase transfer catalyst quaternary ammonium salt, with γ-epoxypropoxy silica gel and calixarenes sodium phenolate in nitrogen or argon gas in 110～120 ℃ of reactions, make the silica gel bonded stationary phase of required calixarenes.
It is coupling agent that the present invention adopts γ-glycidoxy trimethoxy silane (KH-560), under the condition of strong basicity and phase transfer catalysis agent existence, has synthesized the silica gel bonded phase of calixarenes.The gained stationary phase has characterized its structure through infrared spectrum, ultimate analysis and chemical analysis, with methanol-water (70: 30, volume ratio) is moving phase, flow velocity is 0.8mL/min, 4.6 homogenate filling particle diameter is the silica gel bonded stationary phase of the above-mentioned calixarenes of 5 μ m in the stainless steel column of * 150mm, with biphenyl is solute, and recording the post effect under the room temperature is 80,000 plate/rice.With the variety classes solute is probe, solute comprises: palycyclic aromatic, alkyl benzene, fortified phenol and aniline, N-substituted aniline, substituted benzoic acid, carbon bunch, nucleotide, base, sulfonamide and Chinese herbal medicine extract etc., systematically studied the chromatographic performance of stationary phase.On the basis of research chromatographic resolution mechanism, discover on the silica matrix surface, calixarenes and solute exist the containing complexing under the similar solution state, and stationary phase carries out molecular recognition by containing complexing to solute, and molecular recognition and its separation selectivity are closely related.Experimental result shows, the calixarenes bonded stationary phase that adopts this method synthesize has that bonded amount is higher, bonded layer is stablized, method is easy, preparation cost is lower and characteristics such as the preparation method is widely applicable.It not only has traditional ODS reverse-phase chromatography performance, and multiple action sites such as containing complexing, hydrogen bond action, π-π effect and space coupling can be provided simultaneously.Thereby can substitute traditional ODS to a certain extent, and awkward separate substance provides the separation possibility.
Embodiment
The synthetic method that the present invention prepares the silica gel bonded silica stationary phase of calixarenes is as follows:
One, activated silica gel
Take by weighing a certain amount of silica gel in a round-bottomed flask, add 3molmL
-1Hydrochloric acid, silica gel weight (g) and hydrochloric acid volume (mL) are than being 1: 10～1: 15.Soak after 10 hours, refluxed 24 hours, and filtered with G-4 molding sand core funnel while hot, solid is washed till neutrality with distilled water repeatedly, and with twice of washing with acetone, scatter prior to drying by the fire under the infrared lamp to silica gel, 160 ℃ of bakings 6 hours in baking oven are again taken out the back and be chilled to room temperature in exsiccators, go to it in drying pistol fast, the water-bath heating, vacuum drying at least 16 hours is faced and is used preceding taking-up.
Two, the preparation of precursor silica gel
In one condenser pipe is housed, nitrogen ingress pipe, in the drying device of calcium chloride tube and band magnetic agitation, add the new dry toluene (dry toluene with sodium metal reflux the preparation that dewaters) that steams, feed drying nitrogen (nitrogen is in advance through the concentrated sulphuric acid and lime chloride drying), pipette a certain amount of coupling agent γ-glycidoxy trimethoxy silane (KH-560) again, start magnetic stirring apparatus (at a slow speed), stirred 5 minutes, add a certain amount of activated silica gel more fast, silica gel weight (g): coupling agent (mmoL): dry toluene (mL) is generally: 10: 50: 100, drip 3 new triethylamines that steam, oil bath is warming up to 110～120 ℃ rapidly, stirring rate is accelerated simultaneously, reaction is 6 hours under reflux state, stops heating, continues logical nitrogen until room temperature.Cross leakage with the G-4 sand core funnel, solid with toluene and acetone be washed till repeatedly filtrate limpid till, use washing with acetone at last, vacuum drying (80 ℃), the gained precursor silica gel is stored in the exsiccator standby.
Three, the preparation of calixarenes sodium phenolate (the raw material rate of charge is with reference to the 6th)
Take by weighing a certain amount of pre-dry calixarenes in a round-bottomed flask, the new system dry toluene that adds certain volume, load onto reflux condensing tube, nitrogen ingress pipe and calcium chloride tube, feed nitrogen, begin to stir (at a slow speed), add a certain amount of sodium hydride powder (perishable in the air) fast, oil bath, constant temperature to 80 ℃, heated and stirred is after 45 minutes, get calixarenes sodium phenolate suspension, continue next step reaction.
Four, the preparation of the silica gel bonded phase of calixarenes
Add phase transfer catalyst quaternary ammonium salt and precursor silica gel rapidly, quicken to stir, and be warming up to 110～120 ℃, reaction is 24 hours under the reflux state.Stop reaction, cross leakage with the G-4 sand core funnel while hot, and with the toluene wash 2～3 times of heat, use successively again acetone, methyl alcohol, redistilled water cyclic washing to filtrate limpid till, use washing with acetone twice at last, infrared lamp is dried down, gets the stationary phase crude product.
Five, flotation
Get a 50mL graduated cylinder, add 30mL and analyze pure methyl alcohol, add the stationary phase crude product again, ultrasonic Treatment 30 minutes left standstill the tipping supernatant liquor about 5 hours, add same amount methyl alcohol and ultrasonic again,, check flotation effect upper strata liquid microexamination, adjust flotation number of times and methanol usage, general flotation 3～4 times is filtered, use washing with acetone, oven dry (120 ℃) gets the silica gel bonded mutually pure product of calixarenes, behind dry 48 hours of the vacuum gun, be used for ultimate analysis and correlation analysis.
Six, raw material rate of charge
Activated silica gel (g): coupling agent (mmol): calixarenes (mmol): sodium hydride (mmol): phase transfer catalyst (mmol)
Cup [8] aromatic hydrocarbons is generally: 1: 5: 0.2: 1.0: 0.4
Cup [6] aromatic hydrocarbons is generally: 1: 5: 0.3: 1.2: 0.4
Cup [4] aromatic hydrocarbons is generally: 1: 5: 0.4: 1.4: 0.4
Solvent is pressed: silica gel (g): solvent (mL) is: 1: 10
According to the structure of calixarenes, the consumption of calixarenes and sodium hydride can suitably be adjusted, and does not generally depart from 20% of labelled amount, and other consumption is constant.
Seven, bonding concentration
Stationary phase surface calixarenes concentration: α=W/M (μ molg
-1)
W is a stationary phase surface calixarenes weight (g), and M is the calixarenes molal weight, and α is stationary phase surface calixarenes concentration (μ molg
-1).
α is 20～200 μ molg
-1(relevant) with the calixarenes structure.
Adopting γ-glycidoxy trimethoxy silane (KH-560) is coupling agent, and tetrabutyl ammonium bromide is a phase transfer catalyst, and right-tert-butyl group cup [8] aromatic hydrocarbons is raw material, and Kromasil 5 μ m spherical silica gels are matrix, the synthetic silica gel bonded stationary phase example of calixarenes
Preparing right-tert-butyl group cup [8] aromatic hydrocarbons bonding phase by one to four step, this stationary phase is right-and tert-butyl group cup [8] density of aromatic hydrocarbon is: 71 μ molg
-1(, seeing Table 1) according to carbon element content.
Table 1. pair-tert-butyl group cup [8] aromatic hydrocarbons bonding phase bonding concentration
Bonding phase C (%) H (%) bonding concentration (μ molg
-1)
Bonding phase 15.93 2.85 71
Precursor silica gel 8.40 1.42 875
The purposes of stationary phase in high performance liquid chromatography and electrochromatography analysis:
By homogenate method high pressure load the stainless steel performance liquid chromatographic column (4.6 * 150mm) and capillary electric chromatographic column (100 μ m, effective length 20cm, length overall 30cm) compartment analysis implement according to a conventional method.Be used for compartment analysis: alkyl benzene homolog, benzenediol and nitroaniline position isomer, substituted benzoic acid, sulfonamide and palycyclic aromatic.
Claims (1)
1. the preparation method of the silica gel bonded stationary phase of calixarenes, it is characterized in that: under blanket of nitrogen, in activated silica gel: coupling agent: the ratio of dry toluene 10g: 50mmoL: 100mL adds coupling agent γ-glycidoxy trimethoxy silane in the dry toluene, stir, add activated silica gel then, add triethylamine, oil bath is warming up to 110～120 ℃, stir, reaction is 6 hours under reflux state, stops heating, continues logical nitrogen until room temperature; Filter, solid toluene and washing with acetone, vacuum drying makes precursor silica gel; With sodium hydride and calixarenes is reactant, is solvent with the dry toluene, makes the calixarenes sodium phenolate under 70～80 ℃ of conditions; In the presence of the phase transfer catalyst quaternary ammonium salt, with precursor silica gel and calixarenes sodium phenolate in nitrogen or argon gas in 110～120 ℃ of reactions, make the silica gel bonded stationary phase of required calixarenes.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1864852B (en) * | 2006-04-19 | 2012-01-11 | 南昌大学 | A method for preparing chromatogram stationery phase of rhein bonded silica gel |
| CN102091596A (en) * | 2011-01-07 | 2011-06-15 | 郑州大学 | Benzoyl calixarene bonded silica gel stationary phase, preparation method and application thereof |
| CN102101042A (en) * | 2011-01-07 | 2011-06-22 | 郑州大学 | Tetraazacalix [2] arene [2] triazine bonded silica gel stationary phase and preparation method and application thereof |
| CN102091597B (en) * | 2011-01-07 | 2013-03-13 | 郑州大学 | 25,27-di(3-methyl-thio-ethoxy thiadiazole) calix[4]arene stationary phase, preparation method and application thereof |
| CN102489275B (en) * | 2011-12-26 | 2013-07-10 | 郑州大学 | Phenylalanine-substituted calix [4] arene bonded silica gel stationary phase, preparation method thereof, and application thereof |
| CN102489274B (en) * | 2011-12-26 | 2013-07-10 | 郑州大学 | Alanine substituted calix[4]arene bonded silica stationary phase and preparation method and application thereof |
| CN104849380B (en) * | 2014-02-19 | 2016-08-24 | 浙江海洋学院 | A kind of measure the method for aromatic amine in aquatic products contact material |
| CN105771939B (en) * | 2016-04-20 | 2018-03-20 | 郑州大学 | Calixarenes amide derivatives stationary phase and its production and use |
| CN108445136A (en) * | 2018-03-20 | 2018-08-24 | 常州市盛辉药业有限公司 | A kind of high efficiency liquid chromatography for separating and determining 2,4- dichloroacetophenones and 2, the method for 6- dichloroacetophenone isomers |
| CN108445137A (en) * | 2018-03-20 | 2018-08-24 | 常州市盛辉药业有限公司 | A kind of high efficiency liquid chromatography for separating and determining 2, the method for 4- dichloroacetophenones and o-methyl-benzene ethyl ketone |
| CN115611821B (en) * | 2022-10-08 | 2024-03-26 | 山东大学 | Low-dielectric and high-heat-resistance aza calixarene resin, and preparation method and application thereof |
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